Improving the wrinkle resistance of cellulosic textiles

ABSTRACT

A process for finishing cellulosic textile materials with Nmethylol compounds and chlorinated or brominated ethylene carbonates.

United States Patent Inventor Herbert M. Ulrich Vienna, Austria App]. No. 660,612 Filed Aug. 15, 1967 Patented Nov. 2, 1971 Assignee Vereinigte Farbereien Gesellschaft m.b.l-l.

Vienna, Austria Priority Aug. 19, 1966 Austria A7926/66 IMPROVING THE WRINKLE RESISTANCE 0F CELLULOSIC TEXTILES 8 Claims, No Drawings US. Cl 8/116.3, 8/120, 38/144, 8/116.2

[51] Int. Cl ..D06m13/22,

D06m 13/14, D06m 13/38 [50] Field of Search 8/116.3,

[56'] References Cited UNITED STATES PATENTS 3,175,875 3/1965 Gagarine 8/120 Primary Examiner-George F. Lesmes Assistant Examiner-J. Cannon v Attorney-Curtis, Morris & Safford ABSTRACT: A process for finishing cellulosic textile materials with N-methylol compounds and chlorinated or brominated ethylene carbonates.

IMPROVING THE WRINKLE RESISTANCE OF CELLULOSIC TEXTILES The present invention relates to a process for improving the utilitarian properties of cellulosic fibrous materials such as filaments and textiles. In particular it relates to the preparation of materials having increased wrinkle resistance and surface stability by maintaining to a large extent the mechanical properties of the cellulose textile material.

The textile materials with which the present invention is concerned are those which consist of or contain cellulosic fibers, including fibers of regenerated cellulose and of cellulose derivatives which contain reactive or replaceable hydrogen atoms.

In the finishing technique, in particular for fabrics for shirts, different processes are used, which confer to the treated textiles good wash and wear properties. On principle the finishing methods are based upon the cross-linkage of cellulose, if desired, still in the form of fibers or filaments. As cross-linking agent synthetic resin forming as well as cellulosic crosslinking biand polyfunctional N-methylol compounds are used as is the case of the pad-drying-condensation process. The formation of synthetic resins or the cross-linkage of cellulose is heat-catalyzed by substances forming hydrogen ions.

Mainly formaldehyde-precondensates of urea, thiourea or melamine which are hardenable by means of acid are applied. Recently, it has been proposed to use hardenable reactant resins, above all cyclic N-methylol compounds such as dimethylol ethylene urea, dimethylol propylene urea, dimethylol-hydroxyethyl-triazinone and dimethylol-dihydroxy-ethylene-urea for the finishing of cotton and other cellulosic textile materials.

According to the known retention process in the wet state a pre-finish is prepared in the first stage, in the course of which reactive and cellulose-cross-linking reactant resins are applied to the cellulose fibrous material without adding a catalyst.

After intermediate drying, catalyzation of the cellulose cross-linkage is carried out in the second stage at about room temperature by applying a rather concentrated aqueous mineral acid (after-finish state). In order to avoid excessive swelling of the fiber, which occurs during the linking process but only results in an increase in wet crease recovery, it has already been recommended to carry out the catalyzation of the cellulose cross-linkage by using acids in the form of gas such, for example, as hydrogen chloride or concentrated mineral acid which is finely dispersed in inert nonaqueous solvent; the cellulose being impregnated with N-methylol compounds has been brought to a certain content of moisture. Instead of the strong acids, treatment can also be carried out by means of an anhydrous solution consisting of agents splitting off hydrogen chloride in the cold or at moderately elevated temperatures. Then the treated cellulose material is neutralized and washed in most cases by using a warm alkaline bath. Further variations of this retention process in the wet state are: the mineral acid in the nonaqueous solution is replaced to a large extent by a carboxylic acid or at first a cold aqueous dilute mineral acid is used which is converted when a fabric impregnated with the mineral acid is subsequently heated, into the considerably higher concentration desired for the catalyzation of the cellulose cross-linkage with the N-methylol compounds.

The processes for cross-linking cellulose with reactive N- methylol compounds always require a strong acid catalyzation. Since, when cross-linking cellulose in the aqueous swollen state of the fiber, only an increase in wet crease recovery results, the moisture of the fiber is kept during the linkage within certain limits in the described methods for simultaneously obtaining a good dry crease recovery, i.e. the fiber swollen by water, is converted into its former state by adding heat, a fact which happens rather quickly when the pad-drying-condensation is applied, and more slowly when the retention process is applied. The dry cease recovery, however, proves in most cases insufficient, not taking into consideration the technically rather expensive finishing process which is necessary for its execution. Furthermore, the wash and wear properties envisaged have the drawback that a relatively high weakening of the mechanical properties of the cellulose material, such as resistance to tearing and tearing strength and/or resistance to rubbing, is implied so that from the beginning it is generally necessary to work with cotton of especially high quality.

Now it has been found that it is practically possible without or with only a small acid catalysis to obtain a cross-linkage of cellulose fast to washing whilesimultaneously obtaining a high-crease recovery angle in wet and dry states by means ofa retention process at room temperature or, with a shorter retention period at slightly elevated temperatures. The moisture of the fiber during the cellulose crosslinkage is less critical. The present invention is based on the observation that a crosslinking reaction takes place when fibrous materials of cellulosic nature which contain reactive N-methylol compounds are after-treated with chlorinated or brominated ethylene carbonates. The chlorinated or brominated ethylene carbonates are preferably used in anhydrous inert organic media and they are applied to the dry cellulose fiber containing N-methylol compounds. The treatment with the chlorinated or brominated ethylene carbonates evidently leads to the formation of new reactive groups and thereafter in a cross-linking. Furthermore, it has been observed that by subsequent reaction of aqueous baths, preferably of a weakly alkaline nature or of wet steam on the textiles thus treated, a further improvement of the cellulose cross-linkage and thus of the creaseproofing effects is achieved.

Thus, the present invention relates to a process for improving the properties of fibrous materials consisting ofor containing native or regenerated cellulose and preimpregnated with a cross-linking agent, by treating it, in a dry or normal moist state and in the absence or near absence of an acid catalyst, with one or more chlorinated or brominated ethylene carbonates which are dissolved in an inert organic solvent, allowing this treating agent to react on the fibrous materials and then, if desired, eliminating any excess chlorinated or brominated ethylene carbonate as well as the solvent. The material may then be treated, preferably with an aqueous weakly alkaline bath or wet steam, or submitted to washing for a prolonged period of time and finally dried.

As cross-linking agents with which the fibrous materials are preimpregnated, above all the N-methylol compounds, which are appropriate and commonly used for the crease-proof finish of materials made of cellulose, i.e. those of hardenable resins which are capable to form a resin-resin linkage, as well as those of cellulose-linking so-called reactant resins or even mixtures of these resins can be used. Such cross-linking agents suitable for the process of the present invention on the basis of N-methylol compounds are, for example, described in the publication of E. Frieser Chemische Modifikation von Zellulosefasern, in the journal Textil-Praxis," of Feb. 1966, pages 104-112, in the publication of H. E. Bille and H. A. Petersen in the journal Textilveredung," 2, (1967), No. 5, page 243, and in the Handbuch der chemischen Untersuchung der Textilfasertoffe, vol. IV, by H. M. Ulrich, Springer Verlag, Vienna-Heidelberg-Berlin-New York, 1967.

In the process of the present invention the N-methylol compounds can be used in the usual amounts and concentrations. In general an amount of about 3-12 percent by weight, referred to the solid substance and to the dry textile material, is applied when the goods are preimpregnated with N- methylol compounds. If desired, it is also possible for the process of the invention to use considerably smaller amounts of N-methylol compounds for preimpregnation incomparison to conventional wet-state retention processes. Furthermore, it is also possible to apply combinations of resins which are not extremely fast to washing and which are capable of forming a resin-resin linkage, for example dimethylol-urea with reactant resins which lead to an unexpectedly good fastness to washing of the finish. Even when N-methylol compounds which are capable of forming a resin-resin linkage are used alone after treatment with chlorinated or brominated ethylene carbonates according to the process of the present invention results in finishes which are considerably faster to washing than formerly. The term chlorinated or brominated ethylene carbonates," as used in the description of the present invention, is intended to refer to highly chlorinated or brominated products such as di-, triand tetrachloroor bromo-compounds of ethylene carbonate. Chlorinated compounds are preferred. A mixture of difierent highly chlorinated compounds having a content of about 86 to 88 percent by weight dichloroethylene carbonate of 4.5-dichloro-l .3-dioxolone(2) of the formula.

about -12 percent by weight of an unsymmetrical trichlorocompound and small amounts of an unsymmetrical l.ldichloro-ethylene carbonate is especially advantageous and even more favorable than completely chlorinated tetrachloroethylene carbonate. This mixture of chlorinated ethylene carbonate, in the following called chlorodioxolone, has a boiling point (760 torr) of 178 C. and a flash point of 1 18 C., is like the rest ofthe chlorinated ethylene carbonates, a colorless liquid.

In the absence of water the chlorinated or brominated ethylene carbonates are soluble and stable in numerous solvents. Therefore, they are advantageously applied in the process of the present invention in the form ofa solution in an inert anhydrous solvent. For this process, in particular organic compounds such as aromatic hydrocarbons, for example, xylene; aliphatic chlorohydrocarbon such as carbon tetrachloride, trichloro-ethylene, perchloro-ethylene, etc.; acetic acid alkyl esters such as ethyl or butylacetate; ethers, such as ethyl ether, tetrahydrofurane, 4-methyldioxan-l ,3; ethylene carbonate and 1,2-propylene-carbonate are suitable as solvents. Acetic acid and propionic acid can also be used if precautions are taken to exclude water.

Although the chlorinated and brominated ethylene carbonates hydrolyze with water in an elevated temperature by splitting off carbon dioxide and hydrogen chloride, they can also be used in an aqueous medium for the purposes of the present invention. For this purpose the chlorinated or brominated ethylene carbonates, which are insoluble in water, are well emulsified in water by means of a nonionogenic or anionic emulsifier and are applied at low temperatures for example at up to +50 C., i.e., under ice cooling. Under these conditions such emulsions are stable for a sufficiently long period.

Textiles preimpregnated with the cross-linking agents and dried or conditioned to room temperature are preferably treated with the chlorinated or brominated ethylene carbonates in organic media, Solutions of the chlorinated or brominated ethylene carbonates may be applied in optional manner for example by spraying, dipping and squeezing, padding or the like on the fibrous material. The chlorinated or brominated ethylene carbonates can be applied in excess. In general it is, however, sufficient to apply the chlorinated or brominated ethylene carbonates in amounts of about l8 percent by weight to the fibrous material.

The reaction period of the chlorinated or brominated ethylene carbonates in the fibrous material depends on various factors, The temperature has an especially great influence on the reaction period required. Reaction can be effected at room temperature or at an elevated temperature, in particular at about 65 C. When working at relatively low temperatures, for example at room temperature, generally a reaction period of 4-30 hours is necessary. In most cases a retention period of a few hours suffices, for a fabric impregnated with chlorinated or brominated ethylene carbonates and solvents, in order to obtain a high increase in dry crease recovery and simultaneously a good wet crease recovery after the subsequent treatment with an aqueous sodium carbonate solution. If the reaction of the chlorinated or brominated ethylene carbonates is effected at slightly elevated temperatures, for example at 40-65 C., generally a duration of treatment of a few minutes up to a few hours, in most cases about 30 minutes to 2 hours is sufficient.

For carrying out the treatment with chlorinated or brominated ethylene carbonates, the material containing these compounds and, if desired the solvents, are advantageously placed in a hermetically sealed space or the whole is rolled up in a foil. Treatment with chlorinated or brominated ethylene carbonates can also be effected by dipping the fibrous material containing N-methylol compounds into a bath containing the chlorinated or brominated ethylene carbonates in an organic solvent for a period which is required for its treatment, and leaving it there for a whole reaction period. Furthermore, it is possible to treat the fibrous material impregnated with the cross-linking agent in a closed chamber with chlorinated or brominated ethylene carbonates in the form of gas, Due to the higher temperatures used, a particularly short reaction time is sufficient.

After treatment with chlorinated or brominated ethylene carbonates, the portions of these compounds which have not reacted as well as the organic solvents which have been applied with the compounds are removed from the fiber, e.g., by exposing the fibrous material to air or by passing a hot air or steam through the fibrous materials. Then after-treatment is effected by means of aqueous, preferably weakly alkaline, baths or by exposure to wet steam, to which ammonia has preferably been added. Treatment can be carried out in aqueous baths at room temperature or at elevated temperatures up to boiling temperature. It is also possible to combine the aftertreatment with washing suitably by adding a small amount of sodium carbonate. The after-treatment is most desirably carried out at a pH of higher than 7 to 10, preferably at a pH of 7.5 to 9.0.

As tests have shown, chlorinated and brominated ethylene carbonates are capable of reacting by themselves with cellulose by cross-linking. They are, however, not extremely reactive with the hydroxy groups of the cellulose. Under the swelling influence of the chloro-ethylene carbonates only a medium crease recovery in wet state is obtained, which is only slightly improved by prctrcating the cellulose with an alkali or sodium acetate.

If, however, the cellulose material, which is impregnated with reactive and N-methylol compound and submitted to intermediary drying, is submitted to the reaction of anhydrous organic media in which chlorodioxolone" is dissolved, or in chlorodioxolone itself, a material is obtained under conditions envisaged by the process of the present invention having high crease recovery angles in wet as well as in dry state. The behavior, hitherto unknown, of the reactive N-methylol compounds with chlorinated ethylene carbonates in the presence of cellulose which is valid for the "synthetic resin-forming" (cross-linking in itself) as well as for the cellulose crosslinking" types, is of great surprise to the expert.

The unexpected effect which occurs when a dry cellulose fiber is treated according to the process of the present invention with other N-methylol compounds which are added, can be evidenced quite clearly by an increase in the crease recovery. A completely dry cotton fabric impregnated and squeezed off with an aqueous dimethylol-cyclo-ethylene-ureasolution of 5 percent strength and dried for 3 hours at C., cooled in a dessiccator and treated in an closed shaking tube for 2 hours with an anhydrous chlorodioxolone-CCL-solution. yields, after treatment with dilute aqueous sodium hydroxide solution at room temperature or after washing for 4 times at boiling temperature C (according to DIN 53.892), the following crease-angles [warp weft] 2 according to DIN 53.890 (dry) and according to GUTV (wet):

the determination of the crease-angle in wet state was carried out according to the rules of the brand mark rapid iron" ofthe Gutezeichenverband Textilveredlung e. V., Frankfurt/Main (brand mark association for textile finishing, registered association. Frankfurt/Main).

After-treatment with- In dry sta e of the pre-impregnated fabric and after- And washing for 4 times at boiling treated with Gold, aqueous 11/10 temperature C Crease recovery angle chlorodioxolone NaOH (DIN) Crease rlecovgl 'y in dry state (start- 83 (+45% increase)... 124 (+1l7% increase)... 128 (+124% increase).

ing va ue 5 Crease recovery in wet state (start- 123 (+110% increase)... 142 (+14l% increase).

ing value 59).

1 It" can be realized that by after treatment of the treated fabric in an alkaline medium the crease recovery angle in the wet as well as in the dry state increase considerably, which proves that further reactions resulting in a cross-linking of the cellulose take place in the fiber.

The thus'treated cotton fabric showed a soft handle and is resistant to creasing. I

If working is carried out with other N-methylol compounds, similar results are obtained when correspondingly choosing the required time for diffusing the chlorinated or brominated ethylene carbonates in the fiber or for their reaction with the N-Cl-l -BOl-l and cellulose hydroxy groups which are added.

Due to the further development of the process of the invention, one can make use of the fact that with good drying the crease-angle in the dry state is increased, whereas the creaseangle in the wet state increased more rapidly when approaching a normal moisture content. For adjusting a desired proportion of the crease-angle in the dry and wet states, the preferred procedure is that of treating the cellulose material in a completely dry state, most advantageously with less than 1 percent of moisture, in order to achieve a high crease recovery angle in the dry state, followed if desired, by an additional after-conditioning only until the normal degree of moisture of the angle in the wet-state is achieved. According to the process, of the present invention high crease recovery angles in the wet and dry states that are fast to washing at boiling temperature and have a soft handle are obtained while maintaining a relatively good tearing strength and resistance to tearing and rubbing. The treated fabrics maintain their white tint and do not change when ironed hot.or calendered.

An additional advantage ofthe new'process lies in the fact that as additives known products which are often added to the fibrous material for softening and improving the resistance to tearing and rubbing, in particular compounds containing hydroxy, amino or imino groups can be linked simultaneously to the cellulose fast to washing, when treated withchlorodioxolone.

Furthermore, the invention renders possible a special formation of thechlorodioxolone finishing process in connection with dry cleaning by means of organic solvents. For this purpose the cellulose material preirnpregnated with cross-linking agents which may already be in form of clothes, can be treated for example with a chlorodioxolone-containingsolution of an organic dry-cleaning agent which is conventional for dry cleaning, such as perchloro-ethylene, trichloro-ethylene, etc. After removing the organic solvent and'excess chlorodioxolone, for example by means of warm or hot air, the cellulose material is submitted to further treatment with weakly alkaline media and/or to pressure with wet steam. This after-treatment again leads to the new formation of a very high crease recovery angle in the dry state together with a high crease recovery angle in the wet state already described.

When carrying out this process with ready-to-wear clothing it is now possible in a very simple way to produce a wash and wear effect even withthe ready-made clothing. The process is carried out in that a dried fabric impregnated with the corresponding N-methylol compounds is first converted into ready-to-wear clothing (for example trousers having creases, skirts having pleats) which is then treated with a chlorodioxchlorodioxolone by means of hot air. 'By after-steaming, for example in an ironing machine, the desired effect is developed. The pleats and embossed effects which are already made in such a manner by the manufacturer according to the permanent pressing procedure" are fast to washing when later used.

The invention is further illustrated in the following examples and is compared with various working methods which are not part of the invention. The fabrics used in the .tests and their character are summarized in .the following survey. The indications as to percent and quantity are percent by weight and parts by weight unless otherwise stated.

Filaments per 10cm.

A cotton-mollino fabric (Type B) wasimpregnated-with 0.5 percent of an aqueous sodium carbonate solution and'dried at 60 C. After padding with a 5 percent solution of tetrachlorodioxolone-carbon tetrachloride, it is rolled up and aged for 16 hours. Then the fabric is submitted to mild washing and dried.

Crease-angle, 0

Dry (59) Wet (60) After 5 washes to boiling point Furthermore, a sample of the same cotton-mollinp fabric (B) was padded with a 10 percent aqueous dimethylol-urea solution (squeezing effect 105 percent) and dried at C. After dipping for 5 hours in a 20 percent tetrachlorodioxolone carbon tetrachloride solution it was freed from air and submitted to a short cold washing with soap and sodium carbonate and dried.

Crease-angle, w Loss in 2 tearing strength, Dry Wet percent 122 +1o3% 115 +92% -5 Afterwashing lor 5 times to boiling temperature The results shown that tetrachlorodioxolone in the presence of alkali yields only a slight increase in the crease-angle in .wet state and no increase in crease recovery in the dry state. A dry cotton fabric preimpregnated with dimethylol-urea, however,

EXAMPLE 2 Rayon staple (type E) was impregnated with 10 percent aqueous sodium acetate solution (I) alone and 10 percent sodium acetate solution to which 3 percent of dimethylol ethylene urea was added (II) and dried at 70C.

In both cases after-treatment was effected with percent chlorodioxolone-carbon tetrachloride solution and it was removed within 4 hours. In the end a mild weakly alkaline washing was carried out.

- (Warp-l-wett) Clease angle Tearing strength,

(warp+wett) Dry Wet 2 (I) 63 (+5%) 113 (+70%) Dry: 35% increase;

wet: decrease. (II) 77 77 (+24%) 128 (+90%) Wet: No decrease.

The presence of sodium acetate in the fiber, a fact which allows one to assume that it favors the reaction of chlorodioxclone with the hydroxy groups of cellulose by forming hydrochloride, causes a certain increase of the crease-angle in the wet state whereas practically no increase in the creaseangle in the dry state occurred. Already small amounts of a reactant resin in the fiber, besides the sodium acetate, yield another considerable increase of the crease-angle in the wet state and a certain increase of the crease recovery in the dry state.

EXAMPLE 3 Crease-angle Upon reacting with the aqueous bath (II), the crease-angle in dry state is increased in comparison to procedure (I). By washing to boiling temperature, the crease-angle in the dry state is decreased (ill), but in the present case the improved fastness to washing has to be considered as advantage since a ureaformaldehyde-finish is used which normally is to be considered as advantage. The crease-angle obtained does not change. The experiment shows that the finish with dimethylolurea on a rayon staple, which normally has very little fastness to washing can be improved considerably by an after-treatment with chlorodioxolone.

When the same rayon staple fabric was treated with an aqueous solution of a mixture of reactant resin (7 percent of dimethylol-dihydroxy-ethylene-urea) and with cross-linking resin (5 percent of dimethylol-urea), dried under tension and then washed out and dried with a percent chlorodioxolonecarbon tetrachloride solution analogous to the abovedescribed manner, the crease recovery angle in dry state of the cellulose fabric was considerably higher and the crease recovery in the wet state improved as well.

5 Crease-angle Dry Wet War =1e2 War 101 Welt 133 wen 1oo (+00%) 10 EXAMPLE 4 A cotton-poplin-fabric (type C) was treated with a 7 percent aqueous solution of dimethylol-dihydroxy-ethylene-urea for a prolonged period, squeezed to 74.5 percent increase in 15 weight and dried at 70 C. Then the thus treated fabric was aerated for 1 hour. In the second phase the fabric was treated at cold for 15 minutes with a 5 percent chlorodioxolone-carbon tetrachloride solution, squeezed off and rolled up and aged for hours, i.e. submitted to a cold retention process.

2 After aeration it was treated at cold for 30 minutes with a weakly alkaline sodium carbonate containing a nonionogenic linking agent, then it was rinsed with running water and dried.

Crease-angle Dry Wet Warp: 148 Warp: 142.... Wett:150 i Weft: 145.....} (00%) EXAMPLE 5 A cotton fabric (type A) was treated in a padding machine with an aqueous solution ofa mixture of 6 percent dimethylolurea and 6 percent dimethylol-dihydroxy-ethylene-urea (95 percent squeezing effect) and dried for 1 hour at 60 C Then it is treated with a 5 percent by volume of chlorodioxolone- 4 xylene-solution, rolled up and aged for 20 hours. After this it is aerated and treated with hot air C.) for about 10 minutes until free from odor (I).

Then the fabric is washed out with running water, aftertreated for a short period in a handwarm soap-sodium carbonate solution, washed and dried (ll). Then it was washed 10 times at boiling temperature C(DIN (ill).

The experiment shows clearly that only by after-treatment of the treated fabric in an alkaline medium will the creaseangle in the dry state suddenly increase. The crease-angle in the wet state, which was already good at the beginning, is

further increased in the present case. Most striking is the high fastness to washing ofthe treated fabric.

EXAMPLE 6 in this example the finishing according to the process of the present invention by means of the known retention process with aqueous mineral acid, is compared with the pad-dryingcondensation process. The comparative experiments were carried out with a cotton fabric which was, in each instance,

preimpregnated with the same amount of reactant resins.

Preimpregnation of a cotton fabric (type A) divided into three parts:

Parts 1 and 2 were dipped for 30 minutes in a 12 percent aqueous solution of dimethylol-dihydroxy-ethylene-urea.

Part 3 was likewise treated, but 1.2 percent by weight of magnesium chloride (anhydrous) had been added to the solution of reactant resin.

All three fabric samples were squeezed off to 1 percent increase in weight, air dried and after-dried after 2 hours at 60 I C.

Part 1 Retention process in wet state by means of mineral acid.

The preimpregnated dry fabric was introduced for 3 hours into aqueous hydrochloric acid at room temperature (105 g. HCl/l. of bath), then it was squeezed to a 100 percent increase in weight, rolled up and aged for 2 hours. Then the fabric-containing acid was allowed to dry in the air, washed without acid for 1 hour in running water and dried in the air.

Part 2 Retention process by means of chlorodioxolone-CCL.

The preimpregnated dry fabric was introduced into 9 percent chlorodioxolone carbon tetrachloride solution for 1 hour 7 after cooling for 1 hour in the air. After squeezing it is rolled up in wet state and aged for hours. The thus treated fabric was aerated, rinsed 3 times with distilled water and dried in the air. It yields a handle with good resilience.

Part 3 Pad-drying-condensation by means ofa metal salt catalyst.

Condensation was carried out for 4 minutes at 160 C., aging was for 24 hours. Then rinsing with cold water, treating with a soda-soap-solution (2+3 g./l.) at room temperature, after-rinsing with water and drying by hanging in the air was carried out. Crease recovery angles and tearing strength values were measured in all three parallel experiments after finishing had been effected and after washing 10 times at boiling temperature C (DIN).

ment of the two samples (a) and (b) was effected according to the following scheme: Two samples of a cotton-poplin-fabric (D) were impregnated with 150 g./1. of dimethylol-dihydroxyethylene-urea (100 percent) and squeezed to 87 or 84 percent ofincrease in weight.

(a) 87% squeezing- Cuttling of the pleats* Ironing of the pleats and treatment with hot air for 1 hour at Perchloro-ethylene and 5% chloro-dioxolone/l hour- Fresh air/1 hour Hot air/ minutes/ C.-

2 days, aging Product (I) Wetting agent-soda/rinsing and (b) 84% squeezing Drying in the air and calendering treatment with hot air (60 0.)-

Fresh air/2 hours (7% increase in weight) Cutting of the pleats- Perchloro-ethylene and 2% chlorodioxo1one/30 minutes- Fresh air/10 minutes- IIot air/20 minutes/ C.-

Wetting agent-soda/rinsing and drying or wet steam drying or wet steam. Product (11) Product (11).

Crease-angle in dry state (Warp+weft) Sample of a fabric (a) (b) (1) Dry finished (+193%) 78(+128%) (II) Wetting agent soda or wet steam. 157 (+239%) 155 (+236%) Crease-angle in wet state (warp+wcft) N on-finished fabric: 54

Sample of a fabric (a) (b) (1) Dry finished (+176%) 151(+180%) (ll) Wetting agent soda or wet steam 174(+172%) l53(+182%) With this working method the two samples of a fabric were impregnated with a large amount of dimethylol-dihydroxyethylene-urea, squeezed off and after-dried with hot air and then exposed to fresh air for a prolonged period, which causes an increase in the moisture on the fiber. Sample (a) was Crease-angle (Warp+\veft) Loss in tearing strength after washing for 10 times to boiling EXAMPLE 7 This example relates to a warm-retention process in connection with the preparation of permanent pleats. Further treat- 75 treated with stronger concentrated chlorodioxolone solution for a prolonged period in comparison to sample (b). After squeezing off or stripping off, sample (a) was treated with fresh air and hot air for a longer period than sample (12). While (a) as well as (b) showed excellent crease-angles in wet state, only (a) had a good crease recovery in the dry state, whereas (b) showed only a moderate increase in the crease-angle in the dry state. If both fabrics are exposed to an aqueous wetting agent-sodium carbonate solution, in both cases the creaseangle in the dry state is highly increased, i.e. to the same level.

These results show that in spite of the modification of the conditions of treatment during the finishing process, for example, by a stronger moistening by means offresh air with sample (b), the great differences which have occurred in the crease recovery in the dry state with final treatment in a weakly alkaline medium, can be adjusted to the same level. This proves that in the warm retention process a conditioning of the fabric impregnated with N-methylol compounds, i.e. the appearance of hydrochloric acid which is supposed in this connection by hydrolysis of chlorodioxolone, can by no means be the reason for the simultaneous formation of the especially high creaseangle in the dry and wet states.

In both cases the prepared pleats were sharp-edged and fast to mechanical influences as well as to washing, which even led to a softer handle of the fabric. If treatment is effected with wet steam instead of with a wetting-agent-sodium carbonate solution, similar results are obtained.

We claim:

1. A process for finishing cellulosic textile material with the aid ofa reactive N-methylol compound as cross-linking agent which comprises impregnating the material with said methylol compound, drying, applying to the impregnated and dried material a chlorinated or brominated ethylene carbonate for reaction therewith at a temperature of 18 to 65 C. in the absence of an acid catalyst, removing unreacted carbonate, treating the material with wet steam or submitting it to washing with soap and sodium carbonate for a prolonged period, and drying the material.

2. A process as claimed in claim 1, wherein the textile material preimpregnated with a cross-linking agent in the form of ready-to-wear clothing is treated with a solution containing a chlorinated or brominated ethylene carbonate in an organic solvent for dry cleaning, and then the clothing is submitted to a further treatment with wet steam under pressure, unreacted chlorinated or brominated ethylene carbonate and organic solvent being removed by means of hot air.

3. A process as claimed in claim 1, wherein the chlorinated or brominated ethylene carbonate is applied to the textile materials as solution in an inert organic solvent.

4. A process as claimed in claim 1, wherein a mixture of highly chlorinated ethylene carbonates having a content of about 86-88 percent by weight of a symmetrical dichloroethylene-carbonate besides triand unsymmetrical dichloroethylene-carbonates are used.

5. A process as claimed in claim 1, wherein dried textile materials preimpregnated with a cross-linking agent, which have less than 1 percent by weight of moisture are used for the treatment with chlorinated or brominated ethylene carbonates.

6. A process as claimed in claim 1, wherein an aqueous soap-sodium carbonate solution is used for the after-treatment.

7. A process as claimed in claim 1, wherein the reaction of the chlorinated or brominated ethylene carbonates is effected at room temperature within 4 to 30 hours.

8. A process as claimed in claim 1, wherein the reaction of the chlorinated or brominated ethylene carbonates is effected at 40 to 65 C. with 30 to 1 20 minptes 

2. A process as claimed in claim 1, wherein the textile material preimpregnated with a cross-linking agent in the form of ready-to-wear clothing is treated with a solution containing a chlorinated or brominated ethylene carbonate in an organic solvent for dry cleaning, and then the clothing is submitted to a further treatment with wet steam under pressure, unreacted chlorinated or brominated ethylene carbonate and organic solvent being removed by means of hot air.
 3. A process as claimed in claim 1, wherein the chlorinated or brominated ethylene carbonate is applied to the textile materials as solution in an inert organic solvent.
 4. A process as claimed in claim 1, wherein a mixture of highly chlorinated ethylene carbonates having a content of about 86-88 percent by weight of a symmetrical dichloro-ethylene-carbonate besides tri- and unsymmetrical dichloro-ethylene-carbonates are used.
 5. A process as claimed in claim 1, wherein dried textile materials preimpregnated with a cross-linking agent, which have less than 1 percent by weight of moisture are used for the treatment with chlorinated or brominated ethylene carbonates.
 6. A process as claimed in claim 1, wherein an aqueous soap-sodium carbonate solution is used for the after-treatment.
 7. A process as claimed in claim 1, wherein the reaction of the chlorinated or brominated ethylene carbonates is effected at room temperature within 4 to 30 hours.
 8. A process as claimed in claim 1, wherein the reaction of the chlorinated or brominated ethylene carbonates is effected at 40* to 65* C. with 30 to 120 minutes. 